5-carbalkoxy-4-alkyl-2-thiazole-sulfenamides



United States Patent I S-CARBALKOXY- l-ALKYL-Z-THIAZOLE- SULFENAlVIIDES John J. DAmico, Nitro, W. Va., assignor to Monsanto Chemical Company, St. Louis, Mo.', a corporation of Delaware No Drawing. Application December 31, 1956 Serial No. 631,441

2 Claims. (Cl. 2'60302) upon standing under ordinary conditions over a one week period whereas the new compounds are stable indefinitely. They may be prepared by oxidativecondensation of the mercaptothiazole and ammonia.

To a suitable reactor containing 750 ml. of concen-' trated ammonium hydroxide there were added concurrently an aqueous solution comprising 50.8 grams (0.25 mole) of -carbethoxy-4-methyl-2-thiazolethiol (Levi, Gazz. Chem. Ital. 61,.p. 723, 1931), 40.0 grams (0.25 mole) of 25% sodium hydroxide and 100 ml. of water, and 148 ml. (15.1 g./100 ml.) of sodium hypochlorite. The temperature was held at 0-5 C. during the addition which required 90 minutes. stirred for one hour longer and 4 grams of sodium sulfite then added to destroy the excess hypochlorite. The product was collected by filtration, washed with water until free of chloride and air dried at room temperature. The 5-carbethoxy-4-methyl-2-thiazolesulfenamide was obtained in 73.5% yield, M.P. 124-125 C. Analysis gave 13.06% nitrogen and 29.14% sulfur as compared to 12.83% nitrogen and 29.38% sulfur calculated for C'IHIONQOBSQv The reaction mixture was 2,914,535. Patented Nov. 24, 1959' The new compounds'are powerful accelerators with strong delayed action properties for butadiene-styrene copolyrner rubber, natural rubber and other diene hydro-- carbon rubbers. As illustrative of the accelerating activity rubber compositions were compounded comprising Stock- A B Parts by weight 2. 5-carbethoxy 4-methyl-2-thiazole-sulfenamlde 0.

The stocks were vulcanized by heating for various periods of time in a press at 144 C. The modulus, tensile and scorch properties are set forth below:

It is intended to cover all changes and modifications of the examples of the invention herein chosen for purposes 1 of disclosure which do not constitute departures from the spirit and scope of the invention.

What is claimed is:

1. 5-carboloweralkoxy-4-loweralky1- 2 thiazolesulfenamide. 2. 5-carbethoxy-4-methyl-2-thiazolesul.fenamide.

References Cited in the file of this patent UNITED STATES PATENTS 2,419,294 Skaptason Apr. 22, 1947 2,459,736 'Smith Jan. 18, 1949 2,459,763 Heywood Jan. 18, 1949 2,700,659 Carr Jan. 25, 1955 2,704,761 DAmico Mar. 22, 1955 2,721,868 DAmico' 'Oct. 25, 1955 2,766,237

DAmico 0a. 9, 1956 

1. 5-CARBOLOWERALKOXY-4-LOWERALKYL-2-THIAZOLESULFENAMIDE. 